CN105593756A - Display element, photosensitive composition, and electrowetting display - Google Patents

Abstract

The present invention relates to a display element, a photosensitive composition, and an electrowetting display. The display element is provided with a first electrode layer stack, a second electrode layer stack, an accommodation space formed between the first electrode layer stack and the second electrode layer stack, and a partition wall that demarcates the accommodation space. The accommodation space contains at least a polar liquid and a nonpolar liquid that are mutually immiscible. The amount of Li, Na, and K present in the partition wall is 100 ppm or less.

Description

Display element, photosensitive composite and electric moistening display

Technical field

The present invention relates to a kind of display element, photosensitive composite and electric moistening display.

Background technology

Electricity wetting phenomena is the phenomenon of utilizing following situation: for example, and by the non-mixed property on the electrode with hydrophobic surfacePolar liquid and non-polar liquid (being conventionally colored) apply voltage, described hydrophobic surface is to polar liquid (nonpolarity liquidBody) contact angle change.

Utilize the element of this electricity wetting phenomena to demonstrate high brightness and contrast ratio, large visual angle and switching speed fastDeng, in addition, utilize the display element of this phenomenon owing to not needing front lighting or backlight, so power consumption is lower. Therefore,This element is used to multiple smooth application, for example: optical shutter or optical filtering for photoswitch, camera or apparatus for deivation for optical fiberDevice, optically read element, optical waveguide material and video display pixel (videodisplaypixel).

For example, in patent documentation 1, the display element that utilizes phenomenon as above is disclosed.

Prior art document

Patent documentation

Patent documentation 1: Japanese Patent Laid-Open 2013-210479 communique

Summary of the invention

[problem that invention institute wish solves]

Described display element is by according to the having or not of applied voltage, and the existence of non-polar liquid changes, thereby aobviousWord or figure etc. are shown, therefore expect because of the variation of the existence that has or not caused this liquid of applied voltage steadyGround carries out. Along with the requirement of the long lifetime of display element, also require the variation of the existence of this liquid to carry out steadily in the long term.

But, in existing display element, in order to meet these requirements, still there is the further leeway of improvement.

The present invention forms in view of described requirement, and problem is to provide a kind of can make nothing according to having or not of applied voltageThe display element that the existence of polar liquid steadily and steadily in the long term changes.

[technological means of dealing with problems]

Based on this situation, the inventor etc. are artificial solves described problem and carries out active research, found that, by depositingBe that Li, Na in described dividing wall and the amount of K are made as below set value, can solve described problem, thereby complete thisBright.

As described in patent documentation 1 record, utilize in the display element of existing electric wetting phenomena and use black resin (blackEtc. resin) as its dividing wall. In this black resin, comprise black pigment etc., in this pigment, sometimes comprise Li, Na or KSalt etc.

In addition, in the time that the resin that forms existing dividing wall is synthetic, the material that use comprises Li, Na or K etc. conventionally etc. are as urgingAgent.

And then, there is in order to form the display element of being divided the multiple pixel regions that form by multiple dividing walls, there is use sense photosensitivenessComposition, as the situation of the formation material of dividing wall, is formed after film by said composition, uses developer solution to develop, wherebyFormation has the display element of multiple pixel regions. And, in the developer solution now using, conventionally comprise Li, Na or K etc., haveTime in developer solution contained these metals etc. can remain in formed dividing wall.

In addition, in existing dividing wall, in order to improve heat resistance or to control refractive index, (zirconia, titanium oxide etc. carry out height foldingPenetrate rate, silica, hollow silica etc. carries out low-refraction), sometimes add inorganic filler. And, this nothingIn machine filler, conventionally comprise Li, Na or K.

As previously discussed, in existing dividing wall, only otherwise use and comprise especially the material of Li, Na and K, or do not takeThe method of removing Li, Na and K, most of situation comprises Li, Na and K.

On the other hand, the people such as the inventor finds, by as mentioned above, will be present in Li, Na in dividing wall and the amount of KBe made as below set value, can solve described problem.

Configuration example of the present invention is as described below.

[1] display element, it comprises: described the 1st electrode layer heap is piled, is formed to the 1st electrode layer heap, the 2nd electrode layerAnd accommodation space between described the 2nd electrode layer heap and divide the dividing wall of described accommodation space, and

In described accommodation space, at least comprise polar liquid and the non-polar liquid for non-mixed property each other, and

Being present in Li, Na in described dividing wall and the amount of K is below 100ppm.

[2] display element according to [1], being wherein present in Mg in described dividing wall and the amount of Ca is below 300ppm.

[3] according to the display element [1] or [2] described, wherein said dividing wall is the film being obtained by photosensitive composite.

[4] according to the display element described in any one in [1]～[3], wherein said dividing wall is obtained by negative photosensitive compositionThe film obtaining.

[5] according to the display element [4] described, wherein said negative photosensitive composition comprises alkali-soluble polymer, crosslinking agentAnd light trigger.

[6] display element according to [5], wherein said crosslinking agent is the choosing compound that freely contains ethene unsaturated group, containsAt least one chemical combination in the compound of epoxy radicals or oxa-cyclobutyl and the cohort that forms containing the compound of alkoxyalkylThing.

[7] according to the display element [5] or [6] described, wherein said alkali-soluble polymer is to have the free carboxyl group of choosing, phenol hydroxylThe compound of at least one functional group in the cohort that base and silanol group form.

[8], according to the display element described in any one in [5]～[7], wherein said alkali-soluble polymer is to select free acrylic acid treeFat, polyimides, polybenzoxazole, polysiloxanes, polyolefin, resin and the phenolic aldehyde with card many (cardo) skeleton are clearAt least one polymer in the cohort that coating resins forms.

[9] according to the display element described in any one in [5]～[8], the weight average molecular weight of wherein said alkali-soluble polymerBe 1000～100000.

[10] photosensitive composite, it is the dividing wall below 100ppm in order to form the amount of Li, Na and K, described inDividing wall to the 1st electrode layer pile, the 2nd electrode layer heap and accommodation space divide, described accommodation space is formed at the described the 1stBetween electrode layer heap and described the 2nd electrode layer heap and comprise polar liquid and the non-polar liquid for non-mixed property each other.

[11], according to the photosensitive composite [10] described, it is comprise alkali-soluble polymer, crosslinking agent and light trigger negativeType composition.

[12] electric moistening display, it comprises according to the display element described in any one in [1]～[9].

[13] according to the electric moistening display [12] described, it comprises color filter layers.

[effect of invention]

According to the present invention, can provide a kind of can make the existence of non-polar liquid steady according to having or not of applied voltageAnd the display element changing steadily in the long term. In addition, according to the present invention, can provide a kind of light resistance, particularly UV resistantProperty excellence, the display element that amount of gas evolved is few.

Brief description of the drawings

Fig. 1 is the sectional skeleton diagram that represents an example of display element of the present invention.

Fig. 2 is the general view of the dividing wall (clathrate patterned coating film) that obtains in embodiment.

Detailed description of the invention

" display element "

For example Fig. 1 is represented, and display element of the present invention comprises: the 1st electrode layer heap the 11, the 2nd electrode layer heap 12, formationPile the accommodation space 16 between 12 and divide described accommodation space in described the 1st electrode layer heap 11 and described the 2nd electrode layer16 dividing wall 13; And

In described accommodation space 16, at least comprise polar liquid 15 and the non-polar liquid 14 for non-mixed property each other,

Being present in Li, Na in described dividing wall 13 and the amount of K is below 100ppm.

In Fig. 1, the face contacting with described accommodation space 16 of the 1st electrode layer heap 11 is hydrophobicity. Therefore, display element 10In, do not executing in alive situation (Fig. 1 " closing (turnoff) "), non-polar liquid (pigmented fluids) the 14th,The mode of piling 11 surfaces to cover the 1st electrode layer flatly exists. On the other hand, executing alive to this display element 10In situation (Fig. 1 " open (turnon) "), non-polar liquid 14 becomes roughly hemispherical and deposit near dividing wall 13.

As mentioned above, display element of the present invention becomes the existence of non-polar liquid according to having or not of applied voltageChange, by using through painted non-polar liquid, for example, can demonstrate colored state and pellucidity.

In addition the degree of the voltage, display element of the present invention being applied as long as making the existence of non-polar liquid changeVoltage, there is no particular restriction.

Display element of the present invention can be the element with a pixel region (pel), a described pixel region (pel)Be that described accommodation space is formed with divisions such as four dividing walls, but be generally to have, described accommodation space drawn with multiple dividing wallsThe element that divides the multiple pixel regions that form, each pixel region is the side that can carry out full-color demonstration with the display surface side at display elementFormula forms respectively. And, for each pixel region, utilize electric wetting phenomena that the existence of non-polar liquid is changed,The demonstration look of change, display surface side whereby.

<dividing wall>

Described dividing wall is divided the accommodation space being formed between the 1st electrode layer heap and the 2nd electrode layer heap. Described isolationWall is conventionally as long as in the pixel region (pel) of continued presence, and between the pixel region of adjacency, performance does not hinder nonpolarityThe wall of the effect of the contact of liquid, there is no particular restriction.

Therefore, described dividing wall can be as shown in Figure 1, contact with both of the 1st electrode layer heap the 11 and the 2nd electrode layer heap 12,But as shown in Figure 1,, the 1st electrode layer that is present in accommodation space 16 at non-polar liquid 14 is piled 11 sides, also canExist only in the 1st heap 11 sides and do not contact with the 2nd electrode layer heap 12. In the latter case, described dividing wall can be with the 1st11 contacts of electrode layer heap, also can and the 1st electrode layer heap 11 between vacate small gap and exist.

In addition, in the situation that described dividing wall contacts with the 1st electrode layer heap or the 2nd electrode layer heap, can pile with the 1st electrode layer,Or the 2nd electrode layer heap integrated, also can be adhered on the 1st electrode layer heap or the 2nd electrode layer heap.

Being present in Li, Na in described dividing wall and the amount of K is, below 100ppm, to be preferably below 80ppm, more preferablyUnder 50ppm, be particularly preferably below 40ppm. And then, be more preferably present in alkali metal in described dividing wall (Li,Na, K, Rb, Cs and Fr) measure in described scope.

Can be according to applied voltage if the amount of Li, Na and K, particularly alkali metal amount, in described scope, can obtainHave or not and display element that the existence that makes non-polar liquid steadily and steadily in the long term changes. And then, if Li, Na and KAmount, particularly alkali metal amount in described scope, can obtain excellent in light-resistance, dividing wall that amount of gas evolved is few. Therefore,By using this dividing wall, can obtain the display element of durability or demonstration property excellence.

In addition, in dividing wall, exist and exceed Li, the Na and K of amount of described scope, exist easily and produce and leakThe electric bad tendencies such as electric current (spilling the electric current of electric current at the original not position of streaming current).

In addition, in dividing wall, exist and exceed Li, the Na and K of amount of described scope, exist these metals from everyIn wall, leak to the situation in the liquid being present in described accommodation space.

If produce this leakage current or Li, Na and K to spilling in liquid, in the time applying voltage or stop voltageWhile applying, the situation that the existence that existence cannot make non-polar liquid changes as expected, the display element of gained cannot enterThe demonstration that row is distinct, exists easy generation cannot obtain the tendency that the demonstration property such as sufficient contrast decline.

But, according to the present invention, can obtain and be difficult to produce leakage current or Li, Na and K to spilling in liquid, go throughBe difficult to for a long time produce the display element that shows that property declines.

The amount of this Li, Na and K, the particularly dividing wall of alkali metal amount can form with in composition by adjusting this dividing wallThese amounts of metal, or in the time of the various processing forming when dividing wall, do not use the compound that comprises these metals and obtain. And then,Required in the situation that, also can utilize existing known method, form with reducing in composition or dividing wall by self-isolation wallAlkali metal amount and obtaining.

Be present in Mg in described dividing wall and the amount of Ca and be preferably below 300ppm, more preferably below 200ppm,Especially be preferably below 150ppm, be particularly preferably under 100ppm. And then, be more preferably present in described dividing wallPeriodic table of elements group II metal (Be, Mg, Ca, Sr, Ba and Ra) is measured in this scope.

If Mg and Ca amount, particularly periodic table of elements group II metal amount, in described scope, can obtain following demonstrationElement, it is difficult to produce leakage current or periodic table of elements group II metal to spilling in liquid, goes through long-term and is difficult to produceDemonstration property declines, and can the existence of non-polar liquid steadily and steadily in the long term be become according to having or not of applied voltageChange.

The dividing wall of this periodic table of elements group II metal amount can form with the period of element in composition by adjusting this dividing wallTable group II metal amount, or do not use the chemical combination of containing element periodic table group II metal when various processing in the time forming dividing wallThing and obtaining. And then, required in the situation that, also can utilize existing known method, form with combination by self-isolation wallIn thing or dividing wall, reduce periodic table of elements group II metal amount and obtain.

The formation of self-isolation wall there is no by the method that reduces alkali metal amount or periodic table of elements group II metal amount in composition or dividing wallSpecial restriction, for example, can enumerate: Japanese patent laid-open 05-112661 communique, Japanese patent laid-open 08-141308 public affairsReport, Japanese patent laid-open 08-141310 communique, Japanese patent laid-open 08-165313 communique, Japanese patent laid-openThe method of recording in 10-237125 communique, Japanese Patent Laid-Open 2012-136635 communique.

Particularly, the alkali metal amount and the periodic table of elements group II metal amount that are present in described dividing wall can be utilized following enforcementThe method of recording in example is measured.

Light penetration (mensuration wavelength is 400nm) before and after the light fastness test of measuring in the following embodiment of described dividing wallDifference be preferably and be less than 10%, more preferably below 5%.

If dividing wall has this specific character, can obtain following display element, when it is difficult to produce because of manufacture display elementUltraviolet light and the dividing wall that causes is deteriorated or display element is gone through long-term and under demonstration while being exposed in the light such as sunshineFall, and can make the existence of non-polar liquid steadily and steadily in the long term change.

Height (length of the septal direction of the 1st electrode layer heap and the 2nd electrode layer heap, the above-below direction of Fig. 1 of described dividing wallLength) as long as bringing into play the length of effect of the contact that hinders the non-polar liquid between each pixel region, there is no specialRestriction.

In addition, the thickness of described dividing wall is (with the 1st electrode layer heap direction substantially vertical with the septal direction of the 2nd electrode layer heapLength, the length of the left and right directions of Fig. 1) also as long as bringing into play the length of effect of the contact that hinders non-polar liquid,There is no particular restriction, and with regard to the aspects such as the intensity of dividing wall, the thickness of described dividing wall is 1 μ m～50 μ m, is preferably5μm～40μm。

Described dividing wall can be the film of one deck, can be also to comprise black matrix" (blackmatrix, BM) layer, enhancement layerOr the laminate of surface-coated layer etc. In addition, described dividing wall can be the film of not perforate, can be also have clathrate orThe film in the hole of slit-shaped.

[photosensitive composite]

Just can easily make and there is display element of accommodation space being divided with multiple dividing walls the multiple pixel regions that form etc.Aspect, described dividing wall is preferably the film being obtained by photosensitive composite.

In addition, with regard to the amount that can easily obtain Li, Na and K with regard to the aspects such as the dividing wall in described scope, described isolationWall is preferably the film being obtained for the composition below 100ppm by the amount of Li, Na and K, in order to make in the dividing wall of gainedAlkali metal amount and periodic table of elements group II metal amount become described scope, more preferably by comprise with this tittle same degree orThe film that the alkali metal amount that it is following and the composition of periodic table of elements group II metal amount obtain.

Particularly, the upper limit of Li, the Na in photosensitive composite and the amount of K is preferably 120ppm, more preferably 80ppm,Especially be preferably 40ppm, lower limit can be 0.2ppm left and right. Periodic table of elements group II metal amount in photosensitive compositeThe upper limit is preferably 400ppm, and more preferably 200ppm is especially preferably 100ppm, and lower limit can be 0.3ppm left and right.

About these amounts of metal in photosensitive composite, except making sample film by said composition, use beyond this sample film,Can utilize the method identical with the method for recording in following embodiment to measure.

The photosensitive composite of this amount of metal can be by using the amount of alkali metal or periodic table of elements group II metal in described scopeIn raw material be used as the raw material of said composition and obtain, in the case of optionally using amount of metal to exceed the raw material of described scope,Also can, in final stage that obtains composition etc., obtain by utilizing existing known method to reduce described metal.

Described photosensitive composite can be positive light sensitivity composition, also can be negative photosensitive composition, just can easily makeThere is the display element of accommodation space being divided to the multiple pixel regions that form with multiple dividing walls, and acquisition is gone through and is difficult to long-termThe aspects such as the display element that generation demonstration property declines, are preferably negative photosensitive composition.

There is no particular restriction for described photosensitive composite, go through long-term and aspects such as dividing wall that the variation of character is little with regard to obtaining andSpeech, is preferably the composition that comprises alkali-soluble polymer, crosslinking agent and light trigger, and this composition for example can be enumerated JapanThe composition of recording in open patent 2006-154434 communique or Japanese Patent Laid-Open 2007-293306 communique.

Photosensitive composite can easily form dividing wall, described dividing wall to the 1st electrode layer pile, the 2nd electrode layer heap and storageSpace is divided, and described accommodation space is formed between described the 1st electrode layer heap and described the 2nd electrode layer heap and comprises each otherFor polar liquid and the non-polar liquid of non-mixed property, and the amount of the Li of described dividing wall, Na and K is below 100ppm, excellentElect as below 80ppm, more preferably, under 50ppm, be particularly preferably below 40ppm, therefore, this photosensitive composite is suitableShare and make this dividing wall formation composition. This photosensitive composite be preferably comprise alkali-soluble polymer, crosslinking agent andThe minus composition of light trigger.

<alkali-soluble polymer>

There is no particular restriction for described alkali-soluble polymer. In the present invention, so-called alkali-soluble refers to alkaline soluble solution, for example 2.38In the tetramethyl ammonium hydroxide aqueous solution of quality %.

The described alkali-soluble polymer one that can be used alone, also can use two or more, for example alkali-soluble polymer and non-The admixture of the polymer such as alkali-soluble polymer, two or more alkali-soluble polymer.

As described alkali-soluble polymer, just at aqueous slkali, particularly in the tetramethyl ammonium hydroxide aqueous solution of 2.38 quality %The aspect such as dissolubility, be preferably to have and select in the cohort that free carboxyl group, phenol hydroxyl and silanol group form at leastA kind of functional group's compound.

This alkali-soluble polymer be preferably acrylic resin, polyimides, polybenzoxazole, polysiloxanes, polyolefin,There is resin and the novolac resin of card boniness frame.

According to the present invention, using this polymer in the situation that, also can obtain light resistance, particularly ultra-violet resistance excellence,The display element that amount of gas evolved is few.

With regard to the aspects such as the developability of the photosensitive composite of gained, described alkali-soluble polymer utilize gel infiltration tubing stringThe weight average molecular weight that chromatography is measured, specifically utilizes the method for recording in following embodiment to carry out gravimetry averageMolecular weight is preferably 1000～100000, and more preferably 1500～50000.

With regard to the aspects such as the developability of the photosensitive composite of gained, with respect to described photosensitive composite 100 quality %, alkaliThe content of soluble polymer is preferably 5 quality %～60 quality %, more preferably 10 quality %～50 quality %.

Acrylic resin

There is no particular restriction for acrylic resin, with regard to the viewpoint of alkali-soluble, be preferably there is the free carboxyl group of choosing, phenol hydroxylAnd the acrylic resin of at least one functional group in the cohort that forms of silanol group, with regard to the development of the photosensitive composite of gainedProperty etc. aspect, be preferably and use following compound (a) and copolymer (its that obtain as monomer of following compound (b)In, in this monomer, comprise acyclic compound).

Compound (a): there is at least one functional group who selects in the cohort that free carboxyl group, phenol hydroxyl and silanol group formCompound

Compound (b): compound (a) compound in addition

There is no particular restriction for the compound with carboxyl in described compound (a), for example, can enumerate: acrylic acid, metering systemThe monocarboxylic acids such as acid, butenoic acid; The dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid; 2-is along fourthAlkene diacyl oxygen base ethyl-methyl acrylate, 2-succinyl base oxygen base ethyl-methyl acrylate, 2-six hydrogen phthalyl oxygenBase ethyl-methyl acrylate etc. has the methacrylic acid derivative of carboxyl and ester bond. These compounds one that can be used alone,Also can use two or more. These compounds, are preferably acrylic acid, methacrylic acid, 2-six hydrogen phthalyl oxygen base secondYlmethyl acrylate.

There is no particular restriction for the compound with phenol hydroxyl in described compound (a), for example, can enumerate: 3-hydroxy styrenes,4-Vinyl phenol, vinyl-4-HBA ester, 3-isopropenyl phenol, 4-isopropenyl phenol etc. have phenol hydroxylEthene base system monomer. These compounds one that can be used alone, also can be used two or more. In these compounds, be preferably 4-Isopropenyl phenol.

There is no particular restriction for the compound with silanol group in described compound (a), for example, can enumerate: vinyl trimethoxyBase silane, VTES, vinyl tripropoxy silane, vinyl methyl dimethoxysilane, vinyl firstBase diethoxy silane, vinyl methyl dipropoxy silane, γ-(methyl) acryloxy propyl trimethoxy silicane, γ-(firstBase) acryloxy propyl-triethoxysilicane, γ-(methyl) acryloxy propyl group tripropoxy silane, γ-(methyl) acryloylOxygen base propyl group methyl dimethoxysilane, γ-(methyl) acryloxy propyl group methyldiethoxysilane, γ-(methyl) acryloylOxygen base propyl group methyl dipropoxy silane etc. are containing the hydrolysate of the ethene base system monomer of alkoxysilane group. These compounds can be independentUse one, also can use two or more.

Described compound (b) for example can be enumerated: methyl methacrylate, EMA, (methyl) n-butyl acrylate,(methyl) alkyl acrylates such as (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) isopropyl acrylate; (firstBase) (methyl) acrylic acid alcoxyl base ester such as acrylic acid 2-ethoxy ethyl ester, (methyl) acrylic acid 2-methoxyl group ethyl ester; (methyl) acrylic acid(methyl) acrylate of the hydroxyls such as 2-hydroxy methacrylate; (methyl) acrylic acid 2,2, (methyl) third of the halogen atom-containings such as 2-trifluoro ethyl esterOlefin(e) acid ester; (methyl) acrylic acid aryl esters such as (methyl) phenyl acrylate, (methyl) benzyl acrylate; (methyl) acrylic acid glycidolEsters etc. are containing (methyl) acrylate of heterocyclic radical; Diethyl maleate, diethyl fumarate, diethyl itaconate etc. twoCarboxylic acid diesters; Styrene, AMS, a methyl styrene, p-methylstyrene, to methoxy styrene etc. containing secondThe aromatic compound class of thiazolinyl; 1,3-butadiene, isoprene, Isosorbide-5-Nitrae-dimethyl butadiene equiconjugate alkadiene; Acrylonitrile,The polymerizable compound of the nitrile group-containings such as methacrylonitrile; The polymerizable compound that vinyl chloride, vinylidene chloride etc. are chloride; AcryloylThe polymerizable compound of the amide bond such as amine, Methacrylamide; N-phenyl maleimides etc. are containing the polymerization of imideProperty compound; The fatty acid vinyl ester classes such as vinyl acetate; And the represented compound of following formula (6)～formula (8).

[changing 1]

[in formula (6)～formula (8), n represents the natural number more than 1, below 6 independently]

In these compounds, be preferably: methyl methacrylate, EMA, (methyl) n-butyl acrylate, third(methyl) acrylate such as olefin(e) acid 2-methoxyl group ethyl ester, benzyl methacrylate, styrene, N-phenyl maleimide, firstBase acrylic acid 2-hydroxy methacrylate, acrylic acid 2,2,2-trifluoro ethyl ester, described formula (6) and the represented compound of formula (7).

Described compound (b) one that can be used alone, also can be used two or more.

With respect to the total amount 100 quality % of described compound (a) and compound (b), the use amount of described compound (b)Be preferably 5 quality %～95 quality %, more preferably 10 quality %～90 quality %.

Described acrylic resin for example can, by using existing known radical initiator, make described compound (a) and compound(b) in existing known organic solvent, carry out polymerization and obtain.

Polyimides

There is no particular restriction for polyimides, with regard to the viewpoint of alkali-soluble, be preferably there is the free carboxyl group of choosing, phenol hydroxyl andThe polyimides of at least one functional group in the cohort that silanol group forms, is preferably and has this functional group and have following formula(A1) polymer of represented construction unit.

[changing 2]

In formula (A1), R¹For having the bilvalent radical of hydroxyl, X is quadrivalent organic radical. R¹For example can enumerate following formula (a1) instituteThe bilvalent radical representing.

[changing 3]

In formula (a1), R²For singly-bound, oxygen atom, sulphur atom, sulfonyl, carbonyl, methylene, dimethylated methylene base orTwo (trifluoromethyl) methylene; R³Be hydrogen atom, formoxyl, acyl group or alkyl independently. Wherein, R³At least one beHydrogen atom. N1 and n2 are respectively 0～2 integer independently. Wherein, at least one of n1 and n2 is 1 or 2. N1 withN2 adds up in more than 2 situations, multiple R³Can be identical, also can be different.

The represented quadrivalent organic radical of X for example can be enumerated: tetravalence aliphatic alkyl, tetravalence aromatic hydrocarbyl, following formula (1)Represented group. X is preferably the quadrivalent organic radical that is derived from tetracarboxylic dianhydride, more preferably the represented group of following formula (1).

[changing 4]

In formula (1), Ar is trivalent aromatic hydrocarbyl independently, and A is direct bond or bilvalent radical. Described bilvalent radical for exampleCan enumerate: oxygen atom, sulphur atom, sulfonyl, carbonyl, methylene, dimethylated methylene base, two (trifluoromethyl) methylene.

Described polyimides can utilize existing known method, for example, by using diamines and acid anhydrides etc., utilize existing known sideMethod is carried out imidizate and is obtained.

About the polymer with the represented construction unit of described formula (A1), X or R in formula (A1)¹Can have and be selected fromAt least one functional group in the cohort being made up of carboxyl, phenol hydroxyl and silanol group can be also to have this by useFunctional group's compound is as the synthesis material of this polymer, carries out part imidizate and the polymerization with this functional group that obtainsThing.

The acid imide rate of described polyimides is preferably more than 1%, more preferably more than 3%, is especially preferably more than 5%.The higher limit of acid imide rate can be 100%, is preferably 50%, and more preferably 30%. If acid imide rate in described scope,With regard to obtaining the aspect such as polymer of heat resistance and alkali-soluble excellence preferably.

Acid imide rate for example can be measured as follows.

First, measure the infrared absorption spectroscopy of polyimides, confirm the absorption peak of the imide structure being caused by polyimides(1780cm^-1Neighbouring, 1377cm^-1Near) existence. Then,, for this polyimides, at 350 DEG C, carry out 1 hourAfter heat treatment, again measure infrared absorption spectroscopy. To before heat treatment with heat treatment after 1377cm^-1Near peak strength is carried outRelatively. The acid imide rate of the polyimides after heat treatment is made as to 100%, obtains the imidizate of the polyimides before heat treatmentRate={ 1377cm before heat treatment^-11377cm after near peak strength/heat treatment^-1Near peak strength } × 100 (%).In the mensuration of infrared absorption spectroscopy, for example use " Nicolai (NICOLET) 6700FT-IR " (thermoelectron (ThermoElectron)Company manufactures).

Polybenzoxazole

There is no particular restriction for polybenzoxazole, with regard to the viewpoint of alkali-soluble, be preferably there is the free carboxyl group of choosing, phenol hydroxylAnd the polybenzoxazole of at least one functional group in the cohort that forms of silanol group, under being preferably and thering is this functional group and haveState the polymer of the represented construction unit of formula (a5-1).

[changing 5]

In formula (a5-1), X¹For thering is the quadrivalent organic radical of aromatic ring, Y¹For divalent organic base.

In formula (a5-1), X¹In aromatic ring can be any ring that is substituted or is unsubstituted. Substituting group for example can be enumerated-OH ,-COOH, alkyl, alkoxyl, ester ring type alkyl. Be binding on X¹On N and O be for example binding on X¹In fragranceOn adjacent carbon atom on family's ring, form benzoxazole ring. At X¹In comprise plural aromatic ring situation under, multipleAromatic ring can form any structure that links polycyclic system and condensation polycyclic system.

X¹Total carbon number be preferably 6～24, more preferably 6～20, be especially preferably 6～18.

In formula (a5-1), Y¹Be preferably the bilvalent radical that comprises at least one and be selected from the ring in ester ring type ring and aromatic ring, more excellentElect as and there is one～group of tetra-aromatic rings, be particularly preferably the group with two aromatic rings.

In addition Y,¹In contained ester ring type ring and aromatic ring can be any ring that is substituted or is unsubstituted. Substituting group for exampleCan enumerate-OH ,-COOH, alkyl, alkoxyl, alkoxy carbonyl, ester ring type alkyl. At Y¹On comprise plural instituteState in the situation of ring, multiple described rings can form any structure that links polycyclic system and condensation polycyclic system.

Y¹Total carbon number be preferably 4～24, more preferably 4～15, be especially preferably 6～12.

Described polybenzoxazole can utilize existing known method, for example, by making to be selected from dicarboxylic acids, its diester body and dihalide thereofAt least one in object carried out polymerization and obtains with the diamines with two hydroxyls.

About the polymer with the represented construction unit of described formula (a5-1), the X in formula (a5-1)¹Or Y¹Can haveSelecting at least one functional group in the cohort that free carboxyl group, phenol hydroxyl and silanol group form, can be also by making apparatusThere is this functional group's compound as the synthesis material of this polymer, carry out part cyclisation and the polymerization with this functional group that obtainsThing.

The cyclisation rate of described polybenzoxazole is preferably more than 1%, more preferably more than 3%, is especially preferably more than 5%. RingThe higher limit of rate can be 100%, is preferably 50%, and more preferably 30%. If cyclisation rate, in described scope, just obtains resistance toThe aspects such as hot and polymer that alkali-soluble is excellent are preferred.

Cyclisation rate for example can be measured as follows.

First, measure the infrared absorption spectroscopy of polybenzoxazole, confirm the absorption peak (1557cm of benzoxazole ring^-1Near,1574cm^-1) existence. Then,, for this polybenzoxazole, at 350 DEG C, carry out, after heat treatment in 1 hour, again measuring redOuter absorption spectrum. To before heat treatment with heat treatment after 1554cm^-1Near peak strength compares. By gathering after heat treatmentThe cyclisation rate of benzoxazole is made as 100%, obtains the cyclisation rate={ 1554cm before heat treatment of the polybenzoxazole before heat treatment^-11554cm after near peak strength/heat treatment^-1Near peak strength } × 100 (%). In the mensuration of infrared absorption spectroscopyFor example use " Nicolai (NICOLET) 6700FT-IR " (manufacture of thermoelectron (ThermoElectron) company).

Polysiloxanes

There is no particular restriction for polysiloxanes, with regard to the viewpoint of alkali-soluble, be preferably there is the free carboxyl group of choosing, phenol hydroxyl andThe polysiloxanes of at least one functional group in the cohort that silanol group forms, is preferably and has this functional group and make following formula(a4) represented organosilan is hydrolyzed and part condensation and the polysiloxanes that obtains.

[changing 6]

In formula (a4), R¹For the thiazolinyl of the alkyl of hydrogen atom, carbon number 1～10, carbon number 2～10, carbon number 6～15 containing virtueThe group of base, carbon number 2～15 containing the group of epoxide ring or by described alkyl contained 1 or 2 above hydrogen formerSon is substituted by the group (replacement body) that substituting group forms, and has multiple R¹Situation under, respectively can be identical, also can be different;R²For alkyl, the acyl group of carbon number 1～6 or the aryl of carbon number 6～15 of hydrogen atom, carbon number 1～6, there are multiple R²'sSituation, respectively can be identical, also can be different; N is 0～3 integer.

Described substituting group for example can be enumerated and be selected from halogen atom, amino, hydroxyl, sulfydryl, NCO, (methyl) acryloylAt least one in base oxygen base.

With regard to the aspect that makes the crack resistance of dividing wall and hardness and deposit, in polysiloxanes, the content of contained phenyl is with respect to Si100 moles, atom, is preferably 20 moles～70 moles, is especially preferably 30 moles～55 moles. Particularly, this phenylContent can utilize the method for recording in following embodiment to measure.

Polyolefin

There is no particular restriction for polyolefin, with regard to the viewpoint of alkali-soluble, be preferably there is the free carboxyl group of choosing, phenol hydroxyl and siliconThe polyolefin of at least one functional group in the cohort that silane alcohol base forms, is preferably that to have the cyclic olefin of protic polar group poly-Compound. So-called protic polar group refers to that direct bond has hydrogen former on the atom that belongs to the periodic table of elements the 15th family or the 16th familyThe atomic group of son. The atom that belongs to the periodic table of elements the 15th family or the 16th family is preferably oxygen atom, nitrogen-atoms or sulphur atom,Be particularly preferably oxygen atom.

So-called cyclic olefin polymer be have the circulus such as alicyclic ring, aromatic rings and carbon-to-carbon double bond cyclic olefin homopolymers orPerson's copolymer. Cyclic olefin polymer can have by the derivative construction unit of single amount body beyond cyclic olefin.

With regard to the viewpoint of alkali-soluble, the cyclic olefin polymer with protic polar group be preferably there is the free carboxyl group of choosing,At least one functional group in the cohort that phenol hydroxyl and silanol group form, for example, have following formula (A6-1) representedThe polymer of construction unit, particularly has the represented construction unit of formula (A6-1) and the represented structure list of formula (A6-2)The polymer of unit.

[changing 7]

In formula (A6-1), R^a1～R^a4Be independently respectively hydrogen atom or-X_n-R^a5(X is divalent organic base, and n is 0 or 1,R^a5For alkyl, aromatic series base or described protic polar group, alkyl and aromatic series base can have respectively substituting group). R^a1～R^a4In at least one is R^a5For protic polar group-X_n-R^a5Base. M is 0～2 integer, is preferably 0 or 1.

Divalent organic base in X for example can be enumerated: the alkylidene of the carbon numbers such as methylene, ethylidene 1～18, the carbon numbers such as phenylene6～24 arlydene.

R^a5In alkyl be for example the alkyl of the carbon number 1～18 of straight chain shape or branch-like, aromatic series base is for example carbon number 6～24Aromatic series base.

In formula (A6-2), R^b1For the polar group beyond protic polar group, be preferably: the carbon numbers such as acetoxyl group 2～12Acyloxy, methoxycarbonyl, ethoxy carbonyl, positive propoxy carbonyl, isopropoxy carbonyl, n-butoxy carbonyl, 2,2,2-The alkoxy carbonyl of the carbon numbers 2～12 such as trifluoro ethoxy carbonyl, the aryloxycarbonyl of the carbon numbers such as phenyloxycarbonyl 7～24, cyano group,Or the halogen atoms such as chlorine atom.

R^b2For the alkyl of the carbon number such as hydrogen atom, methyl 1～18.

R^b3And R^b4For hydrogen atom.

In addition R,^b1～R^b4Also can be by combining arbitrarily, and together with two carbon atoms of their institute's bonds, form that to comprise oxygen formerSon or nitrogen-atoms are as the heterocycle structure of 3 yuan～5 yuan of ring atom.

M is 0～2 integer, is preferably 0 or 1.

Described polyolefin can utilize existing known method, for example, by making to derive the represented structure list of described formula (A6-1)The monomer of unit carries out polymerization and obtains. And then, also the polymer obtaining by polymerization can be carried out to hydrogenation.

There is the resin of card boniness frame

There is no particular restriction to have the resin of card boniness frame. So-called card boniness frame refers to key on the ring carbon atom that forms circulusHave the skeleton structure of two circuluses, for example can be set forth on the carbon atom of 9 of fluorenes ring bond have two aromatic rings (example:Phenyl ring) structure.

With regard to the viewpoint of alkali-soluble, the resin with card boniness frame is preferably to use has the carboxyl of being selected from, phenol hydroxyl and siliconThe resin of at least one group in silane alcohol base.

On the ring carbon atom that forms circulus, bond has the concrete example of the skeleton structure of two circuluses to enumerate: 9,9-is two(phenyl) fluorene skeleton, 9, two (hydroxy phenyl) fluorene skeletons, 9 of 9-, two (cyano-phenyl or the aminoalkyl phenyl) fluorene skeletons of 9-, have ring9 of oxygen base, two (phenyl) fluorene skeletons of 9-, has 9 of (methyl) acrylic, two (phenyl) fluorene skeletons of 9-.

The resin with card boniness frame can utilize existing known method, for example single amount body with card boniness frame is carried out to polymerization andObtain.

The resin with card boniness frame also can use commercially available product. For example can enumerate: the Ao Gu that Osaka combustion gas chemistry (thigh) is manufacturedSol (Ogsol) CR-TR1, ancient Sol difficult to understand (Ogsol) CR-TR2, ancient Sol difficult to understand (Ogsol) CR-TR3, ancient Sol difficult to understand(Ogsol) CR-TR4, ancient Sol difficult to understand (Ogsol) CR-TR5, ancient Sol difficult to understand (Ogsol) CR-TR6 etc. have card boniness framePetchem.

Novolac resin

There is no particular restriction for novolac resin. Novolac resin can be enumerated and make phenolic compounds react with aldehyde compound and obtainThe resin for example with phenol novolaks structure or cresols novolaks structure obtaining.

Novolac resin is preferably the resin in the tetramethyl ammonium hydroxide that dissolves in 2.38 % by weight.

Novolac resin for example can be enumerated the novolac resin with the represented construction unit of following formula (C1).

[changing 8]

In formula (C1), A is the divalence aromatic series base with phenol hydroxyl, R¹For the alkylidene of methylene, carbon number 2～30,The divalence ester ring type alkyl of carbon number 4～30, the sub-aralkyl of carbon number 7～30 or-R²-Ar-R²-(Ar is two to represented groupValency aromatic series base, R²Be the alkylidene of methylene or carbon number 2～20 independently respectively). In addition, described methylene hasA hydrogen atom can through cyclopentadienyl group, aromatic ring, the group that comprises aromatic ring or have nitrogen-atoms, sulphur atom,The heterocycle of oxygen atom etc. replaces.

R¹In ,-R²-Ar-R²-represented for example can enumerate-CH of group₂-Ph-CH₂-represented group (Ph is phenylene).

The divalence aromatic series base in A with phenol hydroxyl for example can enumerate have phenol hydroxyl phenyl ring, there is the contracting of phenol hydroxylClose polycycle aromatic series base. The condensation polycyclic formula aromatic series base with phenol hydroxyl is for example by condensation polycyclic formula aromatic hydrocarbylContained be binding on hydrogen atom on aromatic rings carbon part or all be substituted by the group of hydroxyl. Condensation polycyclic formula aromatic seriesAlkyl for example can be enumerated naphthalene nucleus, anthracene nucleus, phenanthrene ring.

Novolac resin can use existing known method, for example, use phenol, formaldehyde and acid catalyst or base catalystAnd obtain. In addition, novolac resin can utilize Japan Patent No. 2823057, No. 3729554th, Japan Patent, JapanThe manufacture method of recording in No. 3794598th, patent, No. 3992181st, Japan Patent etc. obtains.

Novolac resin also can use commercially available product. For example can enumerate: the sub-rad of card that Japanese chemical drug (thigh) is manufactured(KAYARAD) CCR-1291H, CCR-1235, PR-40, PR-45, PR-80 that Di Aisheng (DIC) (thigh) manufactures,PR-85 etc.

<crosslinking agent>

Described crosslinking agent is as long as having bridging property functional group, can react with described alkali-soluble polymer and forms crosslinked knotThe compound of structure, there is no particular restriction.

Described bridging property functional group for example can enumerate: oxa-cyclobutyl; Glycidyl ether, glycidol ester group, glycidolThe amino group with epoxy radicals that waits of base; The alkoxyalkyl such as methoxy, ethoxyl methyl; Benzyl oxygen ylmethyl; AcetylOxygen ylmethyl; Benzoxy ylmethyl; Formoxyl; Acetyl group; Dimethylaminomethyl; Diethylamino methyl; Dihydroxy firstBase amino methyl; Dihydroxy ethyl amino methyl; Morpholinyl methyl; The ethene such as vinyl, ethenylidene, (methyl) acryloyl groupUnsaturated group. In these groups, with regard to obtaining case hardness excellence, go through long-term and aspects such as dividing wall that the variation of character is little andSpeech, is preferably ethene unsaturated group, epoxy radicals, oxa-cyclobutyl or alkoxyalkyl.

The described compound containing ethene unsaturated group can be set forth in the chemical combination in molecule with at least two ethene unsaturated groupsThing, is preferably and can enumerates the compound with plural (methyl) acryloyl group.

Particularly can enumerate: trimethylolpropane tris (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycolTwo (methyl) acrylate, TEG two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, BDO two (firstBase) acrylate, butanediol two (methyl) acrylate, propane diols two (methyl) acrylate, trimethylolpropane two (methyl) thirdOlefin(e) acid ester, 1,6-hexylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, neopentyl glycol two (methyl) propyleneAcid esters, three (2-hydroxyethyl) isocyanuric acid ester three (methyl) acrylate, three (2-hydroxyethyl) isocyanuric acid ester two (methyl) propyleneAcid esters, tristane dimethanol two (methyl) acrylate, cyclohexanedimethanol two (methyl) acrylate, bisphenol-A epoxy alkane two(methyl) acrylate, in the diglycidyl ether of bisphenol-A, addition has (methyl) acrylic acid (methyl) acrylate, bisphenol-ATwo (methyl) acryloyl group oxygen base ether, bisphenol-A two (methyl) acryloyl group oxygen base ethyl oxygen base ether, bisphenol-A two (methyl) thirdEnoyl-oxygen ylmethyl ether, Bisphenol F alkylene oxide two (methyl) acrylate, two-trimethylolpropane four (methyl) acrylate,Tetra methylol propane four (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate,Dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, glycerine three (methyl) acrylate, epoxyEthane addition trimethylolpropane tris (methyl) acrylate, ethyleneoxide addition two-trimethylolpropane four (methyl) acrylate,Ethyleneoxide addition pentaerythrite four (methyl) acrylate, ethyleneoxide addition dipentaerythritol six (methyl) acrylate, epoxyPropane addition trimethylolpropane tris (methyl) acrylate, expoxy propane addition two-trimethylolpropane four (methyl) acrylate,Expoxy propane addition pentaerythrite four (methyl) acrylate, expoxy propane addition dipentaerythritol six (methyl) acrylate, ε-Caprolactone addition trimethylolpropane tris (methyl) acrylate, 6-caprolactone addition two-trimethylolpropane four (methyl) acrylic acidEster, 6-caprolactone addition pentaerythrite four (methyl) acrylate, 6-caprolactone addition dipentaerythritol six (methyl) acrylateDeng.

Need only and contain epoxy radicals or oxa-cyclobutyl at molecule containing the compound of epoxy radicals or oxa-cyclobutyl, there is no spyNot Xian Ding, for example can enumerate: KBM303, KBM403 (by SHIN-ETSU HANTOTAI's chemistry (thigh) manufacture), like slope Lai Te (Epolite)M-1230, love slope Lai Te (Epolite) EHDG-L (manufacturing by common prosperity society chemistry (thigh)), (Dongdu changes into (thigh) to PP-101Manufacture), NK oligomeric (NKOligo) EA-1010/ECA (Xin Zhong village chemistry).

The compound with two epoxy radicals or oxa-cyclobutyl for example can be enumerated: like slope Lai Te (Epolite) 40E, like slope LaySpecial (Epolite) 100E, love slope Lai Te (Epolite) 200E, love slope Lai Te (Epolite) 400E, love slope Lai Te (Epolite)70P, love slope Lai Te (Epolite) 200P, love slope Lai Te (Epolite) 400P, love slope Lai Te (Epolite) 1500NP, loveSlope Lai Te (Epolite) 80MF, love slope Lai Te (Epolite) 4000, love slope Lai Te (Epolite) 3002 are (by common prosperity societyChemistry (thigh) manufacture), NC6000 (Japanese chemical drug (thigh) manufacture), pellet is received Cauer (Denacol) EX-212L, Dan NaCauer (Denacol) EX-214L, pellet are received Cauer (Denacol) EX-216L, pellet and are received Cauer (Denacol) EX-850L (allManufactured by long rapids changing into (NagaseChemteX) (thigh)), Sai Luo West Germany (Celloxide) 2021P (Daicel (Daicel)Chemical industry (thigh) is manufactured), GAN, GOT (by Japanese chemical drug (thigh) manufacture), jER828, jER1002, jER1750,JER1007, YX8100-BH30, E1256, E4250, E4275 (manufacturing by Mitsubishi Chemical's (thigh)), BPFG, BPEFG,Ancient Sol (Ogsol) PG100 difficult to understand (manufacturing by Osaka combustion gas chemistry (thigh)), love clone (Epiclon) EXA-9583,HP4032 (manufacturing by Di Aisheng (DIC) (thigh)), EP-4088S, EP-4085S, EP-4080S are (by Ai Dike(Adeka) (thigh)).

The compound with three epoxy radicals or oxa-cyclobutyl for example can be enumerated: VG3101 (Mitsui Chemicals (thigh) manufacture),Special pik (Tepic) S, Te Pike (Tepic) G, Te Pike (Tepic) P (daily output chemical industry (thigh) is manufactured), pelletReceive Cauer (Denacol) EX-321L (long rapids changing into (NagaseChemteX) (thigh) manufacture).

Having four above epoxy radicals or the compound of oxa-cyclobutyl for example can enumerate: Albert (Epotohto) YH-434L(Dongdu change into (thigh) manufacture), EPPN502H, NC3000, NC6000 (by Japanese chemical drug (thigh) manufacture) orLike clone (Epiclon) N695, a HP7200 (manufacturing by Di Aisheng (DIC) (thigh)).

The compound of oxygen heterocycle butyl for example can be enumerated: two [(3-ethyl-3-oxa-cyclobutyl) methyl] biphenyl, 3 of 4,4-, the two (3-of 7-Oxa-cyclobutyl)-5-oxa-nonane, 3,3 '-[1,3-(2-methylene) glyceryl two (oxygen methylene)] two (3-Ethyloxetanes),Isosorbide-5-Nitrae-bis-[(3-ethyl-3-oxa-cyclobutyl) methoxy] benzene, 1, two [(3-ethyl-3-oxa-cyclobutyl) methoxy] ethane of 2-,Two [(3-ethyl-3-oxa-cyclobutyl) methoxy] propane of 1,3-, ethylene glycol bis [(3-ethyl-3-oxa-cyclobutyl) methyl] ether, twoTwo [(3-ethyl-3-oxa-cyclobutyl) methyl] ether of cyclopentenyl, two [(3-ethyl-3-oxa-cyclobutyl) methyl] ether of triethylene glycol, tetremTwo [(3-ethyl-3-oxa-cyclobutyl) methyl] ether of glycol, three ring base dimethylenes in the last of the ten Heavenly stems two two [(3-ethyl-3-oxa-cyclobutyl) methyl]Ether, trimethylolpropane tris [(3-ethyl-3-oxa-cyclobutyl) methyl] ether, Isosorbide-5-Nitrae-bis-[(3-ethyl-3-oxa-cyclobutyl) methoxyl group] fourthAlkane, 1, two [(3-ethyl-3-oxa-cyclobutyl) methoxyl group] hexanes of 6-, pentaerythrite three [(3-ethyl-3-oxa-cyclobutyl) methyl] ether,Pentaerythrite four [(3-ethyl-3-oxa-cyclobutyl) methyl] ether, two [(3-ethyl-3-oxa-cyclobutyl) methyl] ether of polyethylene glycol, two seasonsPenta tetrol six [(3-ethyl-3-oxa-cyclobutyl) methyl] ether, dipentaerythritol five [(3-ethyl-3-oxa-cyclobutyl) methyl] ether, two seasonsPenta tetrol four [(3-ethyl-3-oxa-cyclobutyl) methyl] ether.

Need only and contain alkoxyalkyl at molecule containing the compound of alkoxyalkyl, be not particularly limited, for example, can enumerate:Containing the melamine compound of alkoxyalkyl, containing the benzoguanamine compound of alkoxyalkyl, containing the urea chemical combination of alkoxyalkylThing, containing the phenolic compounds of alkoxyalkyl.

The described crosslinking agent one that can be used alone, also can be used two or more.

Just obtain the composition of photonasty excellence, in addition, obtain and go through long-term and aspects such as dividing wall that the variation of character is little,With respect to described photosensitive composite 100 quality %, the content of crosslinking agent is preferably 5 quality %～80 quality %, more preferably10 quality %～70 quality %, are especially preferably 15 quality %～60 quality %.

<light trigger>

Described light trigger is as long as the compound of initiated polymerization by irradiating the light such as radioactive ray, and there is no particular restriction, can makeWith existing known compound.

This compound can be enumerated: 2,2 '-bis-(2,4-dichlorophenyl)-4,5,4 ' and, 5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2-chlorobenzenesBase)-4,5,4 ', 5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4-3,5-dimethylphenyl)-4,5,4 ', 5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2-Aminomethyl phenyl)-4,5,4 ', 5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-diphenyl-4,5,4 ', 5 '-tetraphenyl-1,2 '-bisglyoxaline, diethoxybenzene secondKetone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone, 2,2-dimethoxy-1,2-hexicholBase ethane-1-ketone, styrax, benzophenone, o-benzoyl yl benzoic acid methyl esters, 4-phenyl benzophenone, 4,4 '-bis-(diethylAmino) benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1,2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-Morpholinyl acetone-1, ethyl ketone, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-, 1-(0-acetyl group oxime), 2,4,6-front threeBase benzoyl-diphenyl-phosphine oxide, two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, 2, two (trichloromethyl)-6-(the 4-first of 4-Oxygen base phenyl)-1,3,5-triazines, 2, two (trichloromethyl)-6-(4-methoxyl group the naphthyl)-1,3,5-triazines of 4-etc.

The described light trigger one that can be used alone, or use two or more.

With regard to obtaining the aspect such as composition of photonasty excellence, with respect to described photosensitive composite 100 quality %, light-initiatedThe content of agent is preferably 0.1 quality %～20 quality %, more preferably 0.5 quality %～10 quality %. By by light triggerContent is made as described scope, and existence can be in the situation that not undermining sensitivity, improves the dividing wall that formed by photosensitive compositeThe tendency of developability.

In described photosensitive composite, and then can be not undermining in the scope of effect of the present invention, allotment organic solvent, antioxidant,The filling such as thermal polymerization inhibitor, surfactant, closely sealed auxiliary agent, dissolubility adjusting agent, viscosity modifier, inorganic filler material,Other additives such as colouring agent.

Described organic solvent can be enumerated: Japanese Patent Laid-Open 2006-201670 communique, Japanese Patent Laid-Open 2012-256023The organic solvent of recording in number communique and Japanese Patent Laid-Open 2014-013413 communique etc.

Described antioxidant can be enumerated: Japanese Patent Laid-Open 2010-117614 communique, Japanese Patent Laid-Open 2010-184961The antioxidant of recording in number communique and Japanese Patent Laid-Open 2013-241554 communique etc.

Described surfactant can be enumerated: Japanese Patent Laid-Open 2010-250109 communique, Japanese Patent Laid-Open 2014-089970The surfactant of recording in number communique and Japanese Patent Laid-Open 2014-048428 communique etc.

Described closely sealed auxiliary agent can be enumerated: Japanese Patent Laid-Open 2012-256023 communique, Japanese Patent Laid-Open 2013-242511The closely sealed auxiliary agent of recording in number communique and Japanese Patent Laid-Open 2014-080578 communique etc.

Described other additives can be enumerated: Japanese Patent Laid-Open 2006-154434 communique or Japanese Patent Laid-Open 2007-293306The compound of recording in number communique etc.

By using described inorganic filler, the hardness of the dividing wall of capable of regulating gained or hotline expansion coefficient.

Described inorganic filler can be enumerated: Japanese Patent Laid-Open 2007-332255 communique, Japanese Patent Laid-Open 2008-242076Number communique, Japanese Patent Laid-Open 2012-198527 communique, Japanese Patent Laid-Open 2013-216737 communique and Japan PatentThe inorganic filler of recording in JP 2014-062195 communique etc.

The preparation method of<photosensitive composite>

Described photosensitive composite for example can by by alkali-soluble polymer, crosslinking agent and light trigger, with other any becomeDivide and mix to prepare. In addition, in order to remove dust, after also each composition evenly can being mixed, utilize filter etc. by instituteThe mixture obtaining filters.

[the formation method of dividing wall]

There is no particular restriction for the formation method of described dividing wall, is preferably and enumerates by being coated with described photosensitive composite and making it hardChange and the method for formation dividing wall.

The formation method of this dividing wall can directly be carried out on the 1st electrode layer heap or the 2nd electrode layer heap, also can prop up at glassAfter holding and carrying out on other supports such as body, metal support or resin support, the dividing wall of gained is arranged to the 1st electricityUtmost point layer heap or the 2nd electrode layer heap are first-class, are preferably on the following electrode layer heap with hydrophobic surface and directly carry out.

There is no particular restriction to form the method for described dividing wall, particularly, and can be by the 1st electrode layer heap or the 2nd electrode layerOn heap or on other supports, be coated with described photosensitive composite, after optionally making it dry, light irradiation makes its sclerosis, therebyObtain dividing wall. In addition, irradiate the described light time, irradiate (exposure) light with the mask of set pattern, then, use alkaliProperty developer solution develops, and optionally heats, and can obtain whereby required form, for example cancellate dividing wall, thereby canEasily make and there is the display element of accommodation space being divided to the multiple pixel regions that form with multiple dividing walls.

These each steps can utilize existing known method to carry out, for example, can enumerate Japanese Patent Laid-Open 2012-256023 public affairsThe method of recording in report.

In the present invention, be preferably the each composition using in these each steps and do not comprise alkali metal or periodic table of elements group II metal,Or comprise with described dividing wall in alkali metal amount and the following alkali gold of periodic table of elements group II metal amount same degree or itsGenus amount and periodic table of elements group II metal amount.

The dividing wall obtaining in described method also can and then carry out existing known minimizing alkali metal amount or the periodic table of elements the 2nd familyThe processing of metal.

The dividing wall obtaining in described method also can and then carry out with inferior surface treatment: to its surface, be preferably two sides,Utilize existing known method of hydrophilizing to carry out hydrophiling, or utilize existing known process for hydrophobicizing to carry out hydrophobicChange.

Method of hydrophilizing for example can be enumerated: with Corona discharge Treatment, plasma treatment or UV ozone treatment, to gainedThe surface of film carry out the method for surfaction; Or by coating or lamination, on the surface of the film of gained, lamination comprises acrylic acidIt is the method for the film of resin or the resin that contains sulphonate-base etc.

Process for hydrophobicizing for example can be enumerated: contain the coupling agent of chain alkyl, fluorine-containing coupling agent or siliceous coupling by utilizationAgent, the surface of the film to gained is carried out surface treatment and is carried out the method for surfaction; Or by coating or lamination, at gainedOn the surface of film, lamination comprises the method containing the film of resin, fluorine resin or the containing silicone resin etc. of chain alkyl.

For example, forming film by described photosensitive composite, this film surface is carried out, in the situation of UV ozone treatment, just canThe aspects such as the easy dividing wall that obtains hydrophily, light resistance, heat resistance, chemical-resistant and high rigidity, when this processingLight exposure is preferably 0.1J/cm²254nm～8J/cm²254nm, more preferably 0.5J/cm²254nm～5J/cm²254nm。

The<the 1 electrode layer heap, the 2nd electrode layer heap>

There is no particular restriction for the 1st electrode layer heap and the 2nd electrode layer heap, is preferably the heap (laminate) that comprises transparent material.

The 1st electrode layer heap and the 2nd electrode layer heap generally include: glass or resin transparency carrier and comprise tin indium oxideThe transparency conducting layer of transparent conductivity materials such as (indiumtinoxide, ITO).

In the situation that using kind electrode layer heap, configure each electrode layer heap in the mode of described transparency conducting layer side subtend.

The 1st electrode layer heap and the 2nd electrode layer heap also can also comprise other layers, for example, at described transparency carrier or transparency conducting layerUpper or these interlayers comprise the existing known layer such as planarization film, passivating film, reflectance coating, dielectric film, hydrophobic film.

The face contacting with described accommodation space of at least one of the 1st electrode layer heap and the 2nd electrode layer heap is preferably hydrophobicity. TheTwo faces that contact with described accommodation space of 1 electrode layer heap and the 2nd electrode layer heap can be respectively hydrophobicity, but in this case,The hydrophobic degree difference of each, is preferably wherein the hydrophobicity of one side higher than the hydrophobicity of another side.

, display element of the present invention is executed in alive situation between not to the 1st electrode layer heap and the 2nd electrode layer heap, excellentElect as the 1st electrode layer heap and the 2nd electrode layer pile up the 1st electrode layer heap or the 2nd electrode layer heap one of them with described storageOn the face of space contact, there is the existing hydrophobic surface of described non-polar liquid.

The electrode layer heap with hydrophobic surface for example can be by comprising the laminate of described transparency carrier and transparency conducting layerSurface, the composition that coating comprises hydrophobic material forms film, or the lamination film that comprises hydrophobic material and obtaining.

This hydrophobic material can be enumerated fluorine material, material, particularly can enumerate: Japanese patent laid-open 04-290746Number communique, Japanese Patent Laid-Open 2010-054785 communique, Japanese patent laid-open 09-208265 communique or Japan Patent spyOpen material of recording in 2012-181513 communique etc., be preferably and can enumerate Japanese Patent Laid-Open 2010-054785 communique, dayThe material of recording in this patent Unexamined Patent 09-208265 communique etc.

<accommodation space>

Described accommodation space can comprise polar liquid and non-polar liquid, as long as the size in this space can not hinder because of applied electricityPress having or not and the existence of the non-polar liquid that causes changes, as long as according to the pixel region of required purposes, institute's wish demonstrationThe size in territory etc. is suitably selected.

<polar liquid>

Described polar liquid is accommodated in described accommodation space. It is non-mixed that polar liquid needs only with the non-polar liquid usingProperty, there is no particular restriction, is preferably the liquid of water white transparency and electric conductivity, particularly, except water, also can makeWith being dissolved with the electrolytical aqueous solution such as lithium chloride or potassium chloride, sodium chloride etc.

Described polar liquid can be used two or more liquid, but conventionally uses a kind of liquid.

<non-polar liquid>

Described non-polar liquid is also accommodated in described accommodation space. There is no particular restriction for non-polar liquid, is preferably substantially notThere is polarity and demonstrate the liquid of electric insulating quality.

Non-polar liquid for example can be enumerated: alkane hydrocarbon, the silicone oils such as side chain higher alcohol, side chain higher fatty acids, octane or decaneDeng hydrophobic liquid.

Described non-polar liquid can use two or more liquid, but conventionally uses a kind of liquid.

Be accommodated in the use amount of the non-polar liquid in a pixel region (pel) as long as suitably adjust according to required purposesCan, being for example preferably can be by the amount of whole covering of the electrode layer heap face of the display surface side of display element.

The non-polar liquid using in the present invention is preferably through painted liquid (pigmented fluids), is preferably at described hydrophobicity liquidIn body, allotment has solubilized or is dispersed in dyestuff in this liquid or the liquid of pigment isochrome material. Pigmented fluids can be transparent,Also can be opaque.

Described dyestuff can be enumerated Japanese Patent Laid-Open 2014-010249 communique or Japanese Patent Laid-Open 2013-228683 communiqueThe pigments of middle record etc., pigment can be enumerated pigment of recording in carbon black or Japanese Patent Laid-Open 2012-181513 communique etc.

Described look material is as long as according to required purposes, and the mode that absorbs the light of set wavelength with non-polar liquid is suitably selected to useCan, the one that can be used alone, also can be used two or more.

In the situation that non-polar liquid contains coloured material, there is no particular restriction for the content of look material, as long as come suitably according to required purposesAdjust, be preferably solubilized or be dispersed in the amount in described hydrophobic liquid, with respect to non-polar liquid 100 quality %,For example be preferably with the amount of 0.01 quality %～30 quality % and allocate.

And then described non-polar liquid also can be optionally, in the scope that does not undermine effect of the present invention, comprise ultra-violet absorber,The various additives such as antioxidant.

" electric moistening display "

As long as electric moistening display of the present invention comprises described display element of the present invention, there is no particular restriction.

Electric moistening display of the present invention is owing to comprising display element of the present invention, so be the demonstration of long-life and demonstration property excellenceDevice.

Electric moistening display of the present invention can be by by the dielectric film using in existing electric moistening display, thin film transistor (TFT) (ThinFilmTransistor, TFT), the existing known layer such as color filter layers, black matrix", according to required purposes, with requiredSequential lamination forms in desired area. As the formation of this electric moistening display, for example, except using display element of the present inventionBeyond part, can be also with Japanese Patent Laid-Open 2013-142753 communique or Japanese Patent Laid-Open 2012-63767 communique inThe identical formation of formation of recording.

Particularly electric moistening display of the present invention, just can manufacture the demonstration that can carry out in display surface side full-color demonstration at low costThe aspects such as device, are preferably and comprise color filter layers.

There is no particular restriction for color filter layers, is not defined as redness, blueness, green, as long as according to required purposes, suitablySelect the layer of cyan, carmetta (magenta), yellow etc. to use.

In addition, color filter layers, as long as according to required purposes, is arranged at desired location, for example, and in electricity profit of the present inventionWet display comprises that, in the situation of color filter layers and TFT, the lamination that can be arranged on described display element of the present invention has TFTSide, also can be arranged on lamination and have the opposite side that the side of TFT is contrary.

[embodiment]

Below, enumerate embodiment, example of the present invention is further specifically described. But the present invention is not subject to these realExecute any restriction of example. In addition,, as long as do not record especially, " part " and " % " is quality criteria.

Based on following condition, measure the utilizing gel infiltration tubing string chromatography of polymer obtaining in following synthesis example and the weight obtainingAmount mean molecule quantity (Mw).

Assay method: gel permeation chromatography

Standard substance: polystyrene

Device: eastern Cao (thigh) manufactures, trade name: HLC-8020

Tubing string: protection tubing string (GuardColumn) H that eastern Cao (thigh) is manufactured_XL-H、TSKgelG7000H_XL、2Root TSKgelGMH_XL、TSKgelG2000H_XLPerson does not successively link

Solvent: oxolane

Sample concentration: 0.7 quality %

Injection rate: 70 μ L

Flow velocity: 1mL/min

1. polymer is synthetic

Synthesizing of [synthesis example 1] polymer (A1)

In reaction vessel, add the propylene glycol methyl ether acetate (propyleneglycolmonomethylether of 160 partsAcetate, PGMEA), be warming up to 80 DEG C. In the container of gained, using as the methacrylic acid of 13 parts of single amount body,The benzyl methacrylate of 46 parts, the styrene of 13 parts, the N-phenyl maleimide of 16 parts, the methacrylic acid of 2 partsThe 2-hydroxyethyl methacrylate of positive butyl ester and 10 parts, two-2 with the azo of 5 parts as polymerization catalyst, 4-dimethyl-pentenNitrile and the solution mixing as the PGMEA of 25 parts of solvent, spend respectively within 2 hours, drip in reaction vessel. DripAfter at 80 DEG C, heat 2 hours, at 100 DEG C, heat 1 hour. Mixed solution after heating is cooled to 23 DEG C, obtains bagSolid component concentration containing polymer (A1) is the PGMEA solution of 35 quality %. The Mw of the polymer (A1) of gained is12000。

Synthetic (polyimides) of [synthesis example 2] polymer (A2)

In there-necked flask, after the gamma-butyrolacton (butyrolactone, γ-BL) of interpolation as the 390g of polymer solvent, will doFor 2,2 '-bis-(3-amino-4-hydroxylphenyl) HFC-236fa of the 120g of diamine compound makes an addition in polymer solvent. Make two amine compoundsAfter thing is dissolved in polymer solvent, add the two O-phthalic acid dianhydrides of 4,4 '-oxygen as the 71g of acid dianhydride. Then, at 60 DEG CLower reaction, after 1 hour, is added the maleic anhydride as the 19g of end-capping reagent. At 60 DEG C so reaction 1 hour after, enterRow heats up, and reacts 4 hours at 180 DEG C, and the solid component concentration that comprises polymer (A2) that obtains whereby about 600g isγ-BL solution of 35 quality %. The Mw of the polymer (A2) of gained is 8000.

Synthetic (the polybenzoxazole predecessor) of [synthesis example 3] polymer (A3)

By diphenyl ether-4 that make 1 mole, 4 '-dicarboxylic acids reacts with the I-hydroxybenzotriazole of 2 moles and the 443.2g that obtainsHexafluoro-2 of the dicarboxylic acid derivatives of (0.90 mole) and 366.3 parts (1.00 moles), two (the 3-amino-4-hydroxylphenyls) third of 2-Alkane, be added to possess thermometer, in the detachable flask of four-hole of mixer, raw material input port and drying nitrogen ingress pipe, toWherein add the METHYLPYRROLIDONE of 3000 parts, make its dissolving. Then use oil bath, at 75 DEG C, react 16 hours.React after 16 hours, add 32.8 parts of (0.20 mole) 5-ENB-2 that are dissolved in 100 parts of METHYLPYRROLIDONEs, 3-Dicarboxylic anhydride, so stir 3 hours and make reaction finish. After reactant mixture is filtered, screening is fed into water/isopropyl alcohol=3/1In the solution of (mass ratio), consequent sediment is filtered and is collected, after fully washing with water, under vacuum, be dried,Obtain whereby polybenzoxazole predecessor (polymer (A3)). The mode that becomes 35 quality % with polymer (A3) concentration is addedAdd γ-BL, obtain γ-BL solution of polymer (A3). The Mw of the polymer (A3) of gained is 15000.

Synthetic (polysiloxanes) of [synthesis example 4] polymer (A4)

In the there-necked flask of 500mL, add the MTMS, 69.41 part (0.35 of 63.39 parts (0.55mol)Mol) phenyltrimethoxysila,e, the 2-of 24.64 parts (0.1mol) (3,4-epoxycyclohexyl) ethyl trimethoxy silane andThe propylene glycol monomethyl ether (propyleneglycolmonomethylether, PGME) of 150.36 parts, at room temperature stirs on one side,One ray flower is added on the phosphorus that is dissolved with 0.338 part (being 0.2 quality % with respect to adding monomer) in the water of 55.8 parts for 10 minutesThe phosphate aqueous solution of acid. Then, flask be impregnated in the oil bath of 70 DEG C, stir after 1 hour, spend 30 minutes oil bath is heated upTo 115 DEG C. Heating up beginning after 1 hour, and the interior temperature of flask reaches 100 DEG C, starts to add 2 hours (flasks of thermal agitation from nowInterior temperature be 100 DEG C～110 DEG C). Methyl alcohol and hydration meter as accessory substance in reaction distill out 115 parts. In the polymerization of gainedIn the PGME solution of thing (A4), the mode that becomes 35 quality % with polymer (A4) concentration is added PGME, obtains poly-The PGME solution of compound (A4). The Mw of the polymer (A4) of gained is 5000, with respect to 100 moles, Si atom,Phenyl content is 35 moles.

In addition, the content of the phenyl in polymer (A4) is to use " JNM-ECS400 " (NEC's (thigh) manufacture)Measure²⁹Si-NMR spectrum, according to the peak area of the Si of this phenyl institute bond and the not peak area of the Si of bond of phenylRecently obtain.

Synthetic (polyolefin) of [synthesis example 5] polymer (A5)

In the 1000mL of nitrogen replacement autoclave, add the 8-carboxyl Fourth Ring [4.4.0.1 of 60 parts^2，5.1^7，10] 12-3-alkene,N-phenyl-(5-ENB-2, the 3-dicarboxyl acid imide) of 40 parts, 2.8 parts 1,5-hexadiene, (the equal front three of 1,3-bis-of 0.05 partPhenylimidazole pyridine-2-subunit) PGMEA of (tricyclohexyl phosphine) benzal chloride ruthenium and 400 parts, stirs while at 80 DEG CUnder carry out 2 hours polymerisations, obtain contain polymer (A5 ') polymer solution.

In this polymer solution, add two (tricyclohexyl phosphine) ethyoxyl methylene chlorides of 0.1 part as hydrogenation catalystRuthenium, is blown into hydrogen 5 hours with the pressure of 4MPa, carries out after hydrogenation, adds the active carbon powder of 1 part, stirs on one sideAt 150 DEG C, be blown into hydrogen 3 hours with the pressure of 4MPa on one side. Then, utilizing aperture is the fluororesin system filtration of 0.2 μ mDevice filters, and by Activated carbon separation, the hydride that contains polymer (A5 ') that obtains whereby 490 parts is polymer (A5)Hydrogenation solution. The solid component concentration of the hydrogenation solution that contains polymer (A5) herein obtaining is 21 quality %,The output of polymer (A5) is 102 parts. Utilize rotary evaporator that the hydrogenation solution of the polymer of gained (A5) is carried outConcentrated, solid component concentration is adjusted into 35 quality %, obtain the solution of polymer (A5). The polymer (A5) of gainedMw is 4000.

The preparation (blocking many resins) of [preparation example 6] polymer (A6)

CR-TR5 (Osaka combustion gas chemistry (thigh) manufacture) as the PGME solution that blocks many resins is that solid constituent is 52.7The goods that quality %, solid constituent acid number are 135KOHmg/g. Weigh the CR-TR5 of 100 parts, add therein 50.57 partsPGME stir. Obtaining in this way solid component concentration is the solution of the many resins of card (A6) of 35 quality %.

Synthetic (novolac resin) of [synthesis example 7] polymer (A7)

Being provided with in the flask of thermometer, cooling tube, fractionating column and agitator, add 94.1g (1.0 moles) phenol,The 92 quality % PARA FORMALDEHYDE PRILLS(91,95)s of the methyl iso-butyl ketone (MIBK) of 400g, the water of 96g and 32.6g (being scaled 1.0 moles with formaldehyde). ?Wherein, stir while add the p-methyl benzenesulfonic acid of 3.4g. Then, at 100 DEG C, react 8 hours. After reaction finishes,The pure water that adds 200g, is transferred to intrasystem solution in separatory funnel, separates and removes water layer. Then, organic layer is washedTill demonstrating neutrality to washings, then, under heating decompression, in organic layer, remove solvent, obtain the novolaks of 140gResin (polymer (A7)). The Mw of the polymer (A7) of gained is 2000. Use gained polymer (A7) andPGMEA and obtain the solution of the polymer that solid component concentration is 35 quality % (A7).

According to by Fourier transform infrared spectrophotometer (FourierTransform-InfraredSpectroscopy, FT-IR)The mensuration chart obtaining, compares with raw material, can confirm the absorption (2800cm being come by the flexible of methene key^-1～3000cm^-1), and then, cannot find the absorption (1000cm being come by aromatic ether^-1～1200cm^-1). Can reflect according to these resultsBe decided to be: in this synthesis example, do not produce hydroxyl dehydration etherification reaction (hydroxyl disappearance) each other, obtain the phenolic aldehyde with methene keyVarnish gum.

2. dividing wall forms the preparation with photosensitive composite

By being scaled with polymer (A1) solution, 70 of the polymer (A1) obtaining in the described synthesis example 1 of 100 partsCrosslinking agent (B1), the light trigger (C) of 5 parts, the closely sealed auxiliary agent (D) of 5 parts and the surfactant (E) of 1 part of partMix, obtain the composition 1 as solution.

Similarly, with the composition shown in following table 1, each composition is mixed, obtain whereby composition 2～composition 13. GroupIn compound 2～composition 13, the mode that also becomes the amount of following table 1 with the amount of the polymer in said composition is used described acquisitionPolymer solution. In addition, Details as Follows states described in table 2 for the each composition in table 1.

[table 1]

[table 2]

[embodiment 1]

3. making of dividing wall

One side possesses on the ITO layer of chip glass of the ITO layer that 100nm is thick therein, the composition 1 shown in coating table 1,Utilize the heating plate at 110 DEG C, to carry out 5 minutes heat treated (prebake conditions), height of formation (is equivalent to the above-below direction of Fig. 1The length of direction) be the film of 25 μ m～35 μ m. For formed film, via pattern mask, use stepper(Nikon (Nikon) (thigh) is manufactured, model " NSR-2005i10D "), exposes the amount of ultraviolet shown in table 3.Film after exposure is flooded to 90 seconds (development treatment) in the aqueous solution of the tetramethyl ammonium hydroxide that contains 2.38 quality %, continueAnd, wash processing. Then, utilize baking oven at 220 DEG C, to carry out 1 hour heat treated, to its surface, use desk-top lightSurface processing device (goods name PL16-110, SEN special light sources (thigh) is manufactured) carries out the UV ozone of Cooper-Hewitt lampProcess (light exposure: 3J/cm²254nm), making whereby live width is that 10 μ m, grid are spaced apart 50 μ m, (phase highlyWhen the length of the direction of the above-below direction in Fig. 1) be the dividing wall (clathrate patterned coating film) of 20 μ m. By gained everyPlane from wall (clathrate patterned coating film) is shown in Fig. 2.

In addition value (the J/cm of the light exposure in the present invention,²254nm) when irradiated ultraviolet ray is scaled to 254nmLight amount, the value (mJ/cm of light exposure²365nm) be light amount when irradiated ultraviolet ray is scaled to 365nm.

4. making of display element

As substrate, use one side therein to possess the ITO layer that 100nm is thick and on this ITO layer, possess 450 μ m thickThe thickness of hydrophobic film (amorphism fluoropolymer polymer " AF1600 ", company of Du Pont (DuPont) manufacture) be that 0.7mm is thickGlass plate, be coated with the composition 1 shown in table 1 on the hydrophobic film of this substrate, in addition, with described " 3. dividing wallMake " identical mode, height of formation (being equivalent to the length of the direction of the above-below direction of Fig. 1) is that 20 μ m, live width are 10μ m, grid are spaced apart the dividing wall of 50 μ m. In the zoning (pel) of surrounding at the dividing wall by formed, injecting respectivelyLook oil (is dissolved with the liquid of sudan black (Sudanblack) B (manufacturing with the pure pharmaceutical worker's industry of light (thigh)) of 0.1wt% in octaneBody), the substrate with dividing wall of gained is put into water. Then, use one side therein to possess the ITO layer that 100nm is thickGlass plate 2, the ITO layer of this glass plate 2 becomes the substrate-side with dividing wall, and configures in the mode contacting with dividing wall.Then, utilize photo-hardening epoxy adhesive, the contact site of the ITO layer of dividing wall and glass plate 2 is sealed, whereby systemBecome the display element in substrate center portion with more than 100 pels.

[embodiment 2～embodiment 11 and comparative example 1～comparative example 2]

Except using the composition shown in table 3, in the mode identical with embodiment 1, form respectively dividing wall and demonstrationElement.

5. evaluate

Utilize following methods, the dividing wall obtaining in embodiment and comparative example and display element are evaluated. Show the result inIn table 3.

5-1. shape

Utilize electron microscope, the section shape of the dividing wall obtaining in described embodiment and comparative example is observed, utilization is swept(Hitachi's new and high technology (thigh) is manufactured, form to retouch formula electron microscope (scanningelectronmicroscope, SEM)" S-4200 ") measure dividing wall height (being equivalent to the length of the direction of the above-below direction of Fig. 1), contact with ITO layerThe width (top width) of the side with contacting with ITO layer of width (bottom width), dividing wall of the dividing wall dividing wall that is opposition side.

The mensuration of 5-2. amount of metal

On the dividing wall obtaining, cut the big or small of vertical 1cm, horizontal 1cm, thick 20 μ m in described embodiment and comparative exampleTest film, uses this test film is dissolved in to the solution forming in chloroazotic acid, utilizes icp ms (InductivelyCoupledPlasmaMassSpectrometer, ICP-MS) (Agilent (Agilent) 7500, Agilent science and technology (AgilentTechnology) (thigh) manufactured), measure amount of metal contained in this test film.

The mensuration of the transmitance of 5-3. cured film (dividing wall)

Upper at glass substrate " healthy and free from worry (Corning) 7059 " (manufacture of healthy and free from worry (Corning) company), be coated with respectively table 1Shown composition, utilizes heating plate at 110 DEG C, to carry out 5 minutes heat treated (prebake conditions), and height of formation (is equivalent to figureThe length of the direction of 1 above-below direction) be the film of 25 μ m～35 μ m. For formed film, use stepper (Buddhist nunHealth (Nikon) (thigh) is manufactured, model " NSR-2005i10D "), the amount of ultraviolet shown in table 3 is exposed. To expose to the sunFilm after light floods 90 seconds (development treatment) in the aqueous solution of the tetramethyl ammonium hydroxide that contains 2.38 quality %, then,Wash processing. Then, utilize baking oven at 220 DEG C, to carry out 1 hour heat treated, to its surface, use desk-top optical surfaceTreating apparatus (goods name PL16-110, SEN special light sources (thigh) is manufactured) carries out the UV ozone treatment of Cooper-Hewitt lamp(light exposure: 3J/cm²254nm), made thereby cured film.

Use spectrophotometer " 150-20 type dual-beam " (Hitachi (thigh) manufactured), with 400nm～800nmThe wavelength of scope measure the light penetration [%] of the glass substrate with this cured film. By minimum light penetration nowThe value of (initial light penetration) is shown in Table 3.

The weather-proof machine FDP of the ultraviolet fluorescent lamp (light source that uses this Accelerated Life machine (SugaTestInstruments) (thigh) to manufactureFor SUGA-FS40, radiation illumination is 28W/m²(wavelength is 270nm-700nm, and peak wavelength is 313nm), testTemperature is 60 DEG C), evaluate the light resistance of the cured film of described acquisition.

Particularly, the ultraviolet ray that utilizes identical test machine to carry out 168 hours is irradiated, and measures ultraviolet postradiation cured filmLight penetration (test after light penetration).

In addition, calculate the difference of light penetration according to following formula.

Light penetration after difference (the %)=test of light penetration-initial light penetration

5-4. is derived from the evaluation of the amount of gas evolved in the cured film (dividing wall) after light fastness test

The amount of gas evolved being derived from the postradiation cured film of the ultraviolet ray obtaining in 5-3. is evaluated.

Particularly, use purge and trap (purgeandtrap) gas chromatograph-mass spectrometer (GasChromatographyMassSpectrometry, GC-MS) (Japanese analytical industry (thigh) is manufactured, automatically P&T device JTD-505), measure instituteState the amount of gas evolved producing when ultraviolet postradiation cured film heats 15 minutes at 230 DEG C.

The evaluation of the operating state of 5-5. display element

There is a pair of ITO interlayer of dividing wall, colored oil and water to apply to the clamping of the display element obtaining in embodiment and comparative exampleThe DC voltage at 10V/10 μ m interval. The display element obtaining in embodiment is by applying 100 of substrate center portion pelsVoltage, colored oil shrinks (to hemispherical variation) and sees through the back side, and in the situation that stopping voltage and applying, all pels are extensiveBe painted demonstration again.

Applying with stopping of applying of described DC voltage, as a circulation, is cycled to repeat these 100 times, follows repeating thisEncircle stopping under state that voltage applies after 100 times, by all pels, exceed and in the pel of 8 one-tenth, do not produce painted demonstrationThe operating state that damaged situation is judged as display element is " well ", by 2 one-tenth above～be less than in the pel of half and producedThe damaged state of painted demonstration is judged as the operating state " slightly good " of display element, will in pel more than half, produceThe operating state that the damaged situation of painted demonstration is judged as display element is " bad ".

[table 3]

6. evaluation result

The dividing wall obtaining in embodiment 1～embodiment 11 before and after the light fastness test, light penetration with low uncertainty, in addition,After light fastness test, amount of gas evolved is also few, therefore think, even if the display element that comprises this dividing wall is after being exposed in light,Durability or demonstration property excellence. And then through confirming, the display element obtaining in embodiment 1～embodiment 11 is repeatingState and circulate after 100 times, still in pel more than half, do not produce the damaged of painted demonstration. Particularly embodiment 1～embodiment3 and embodiment 5～embodiment 11 in the display element that obtains repeating, after described circulation 100 times, still to exceed 8 one-tenthPel in do not produce the damaged of painted demonstration. Known, the display element obtaining in embodiment can make colored oil (nonpolarityLiquid) existence change steadily and steadily in the long term.

On the other hand, the display element obtaining in comparative example 1 and comparative example 2 is due in the evaluation of the operating state of display element,All the colored oil in the time stopping voltage and apply is abnormal to seeing in roughly hemispheric variation (contraction movement), and half withOn pel in produce the damaged of painted demonstration, so that evaluation result is is bad. In addition, in comparative example 1 and comparative example 2, obtainThe amount of gas evolved of dividing wall after due to light fastness test many, so think, the display element that comprises this dividing wall is being exposed toAfter in light, easily produce and heave etc., durability or demonstration property insufficient.

[explanation of symbol]

10: display element

11: the 1 electrode layer heaps

12: the 2 electrode layer heaps

13: dividing wall

14: non-polar liquid

15: polar liquid

16: accommodation space (pixel region (pel))

20: be formed at the dividing wall on ITO layer

21: dividing wall

22:ITO layer

23: pel

Claims (13)

1. a display element, it comprises: described the 1st electrode layer heap is piled, is formed to the 1st electrode layer heap, the 2nd electrode layerAnd accommodation space between described the 2nd electrode layer heap and divide the dividing wall of described accommodation space, and

In described accommodation space, at least comprise polar liquid and the non-polar liquid for non-mixed property each other,

Being present in Li, Na in described dividing wall and the amount of K is below 100ppm.

2. display element according to claim 1, being wherein present in Mg in described dividing wall and the amount of Ca is 300ppmBelow.

3. display element according to claim 1 and 2, wherein said dividing wall is to be obtained by photosensitive compositeFilm.

4. according to the display element described in any one in claims 1 to 3, wherein said dividing wall is by negative-type photosensitive groupThe film that compound obtains.

5. display element according to claim 4, wherein said negative photosensitive composition comprise alkali-soluble polymer,Crosslinking agent and light trigger.

6. display element according to claim 5, wherein said crosslinking agent is the change that choosing freely contains ethene unsaturated groupAt least one in compound, the cohort that forms containing the compound of epoxy radicals or oxa-cyclobutyl and containing the compound of alkoxyalkylPlant compound.

7. according to the display element described in claim 5 or 6, wherein said alkali-soluble polymer for have the free carboxyl group of choosing,The compound of at least one functional group in the cohort that phenol hydroxyl and silanol group form.

8. according to the display element described in any one in claim 5 to 7, wherein said alkali-soluble polymer is for selecting freelyAcrylic resin, polyimides, polybenzoxazole, polysiloxanes, polyolefin, resin and the phenolic aldehyde with card boniness frame are clearAt least one polymer in the cohort that coating resins forms.

9. according to the display element described in any one in claim 5 to 8, the weight of wherein said alkali-soluble polymer is flatAverage molecular weight is 1000～100000.

10. a photosensitive composite, it is the dividing wall below 100ppm in order to form the amount of Li, Na and K, described inDividing wall to the 1st electrode layer pile, the 2nd electrode layer heap and accommodation space divide, described accommodation space is formed at the described the 1stBetween electrode layer heap and described the 2nd electrode layer heap and comprise polar liquid and the non-polar liquid for non-mixed property each other.

11. photosensitive composites according to claim 10, it draws for comprising alkali-soluble polymer, crosslinking agent and lightSend out the minus composition of agent.

12. 1 kinds of electric moistening displays, it comprises according to the display element described in any one in claim 1 to 9.

13. electric moistening displays according to claim 12, it comprises color filter layers.